TWI246886B - Fungicidal mixtures based on amide compounds and morpholine or piperidine derivatives - Google Patents

Abstract

Fungicidal mixtures comprise as active components (a) an amide compound of the formula I: A-CO-NR1R2, in which A, R1 and R2 are as defined in the description, and (b) dimethomorph or flumetover, and/or (c) a valinamide of the formula III, in which, R13 is C3-C4-alkyl and R14 is naphthyl or phenyl, where the phenyl radical is substituted in the 4-position by a halogen atom, a C1-C4-alkyl or C1-C4-alkoxy group, and/or (d) benalaxyl, ofurace, metalaxyl, furalaxyl or oxydixyl, and/or (e) 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea in a synergistically effective amount.

Description

1246886 V. INSTRUCTIONS (i) The present invention relates to a fungicidal mixture for controlling harmful fungi, and to a method for controlling harmful fungi using the mixture. W0 9 7/ 0 8 9 5 2 describes a mixture of the indoleamine compound of the formula I and the active ingredient known as an acaricide, fenaze (f e n a z a q u i η ).

AC〇-NR]R2 I wherein A is an aryl group or an aromatic or non-aromatic 5- or 6-membered heterocyclic ring containing 1 to 3 hetero atoms selected from 0, N and S; wherein aryl or heterocyclic ring May or may not have 1, 2 or 3 substituents independently selected from the group consisting of an alkyl group, a halogen, a CHF2, a CF3, an oxy group, a halogenated alkoxy group, a sulfur-burning group, a pyrogenic base group, and a burned S-disk base. R1 is a hydrogen atom; R2 may or may not have 1, 2 or 3 independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, ring a phenyl or cycloalkyl group having a substituent of an alkenyl group, a cycloalkoxy group, a cycloalkenyloxy group, a phenyl group and a phenyl group, wherein the aliphatic and cycloaliphatic groups may be partially or completely halogenated and/or a cycloaliphatic group may be used. Substituted with 1 to 3 alkyl groups and wherein the phenyl group may have 1 to 5 halogen atoms and/or 1 to 3 are independently selected from the group consisting of alkyl, i-alkyl, alkoxy, haloalkoxy, alkylthio And a substituent of the i-alkylthio group, wherein the decylamine phenyl group may or may not be substituted with or without one or more alkyl groups and/or may have a saturated heteroatom selected from the group consisting of 0 and S Ring condensation. These mixtures are described as being particularly effective against grape cultivars (B 〇 t r y t i s ). 2 One of the objects of the present invention is to provide a particularly effective mixture for controlling harmful fungi, especially for fungi having certain signs.

1246886 V. INSTRUCTIONS (2) It has surprisingly been found that this object can be achieved by including a synergistically effective amount of the above formula I amide compound as the active ingredient and the following ingredients as a mixture of further fungicidal active ingredients. b) Formamide II selected from the group consisting of the compounds Ila and lib:

_)

m > and / or

c) Chloroguanamine of formula III: H3C - CH - CH3 (HI) ο o 9Hs 1丨Π ' R13〇 - c - NH - CH - C NH - CH R14 wherein R13 is C3_4 alkyl, and

Page 8 1246886 V. INSTRUCTIONS (4) 丨 and/or! e) l-(2-Cyano-2-oxiranimidoyl)-3-ethyl oxime (V): ί I H3CCH2 -NHCONH-C(CN)DiN〇CH3 (V) The mixtures according to the invention have a synergistic effect and are therefore particularly suitable for controlling harmful fungi, especially fungus fungi in vegetables and grapes. For the purposes of the present invention, halogens are fluorine, gas, bromine and iodine and especially fluorine, chlorine and desert.

π alkyl π - the word contains a straight chain and a branched alkyl group. It is preferably a linear or branched Ch2 alkyl group, and especially a Ch alkyl group. Examples of the alkyl group are, for example, methyl, ethyl, propyl, 1-decylethyl, butyl, 1-mercaptopropyl, 2-mercaptopropyl, 1,1-dimethylethyl, n-pentyl Base, 1-methylbutyl, 2-methylbutyl, 3-decylbutyl, 1,2-dimercaptopropyl, 1,1-dimethylpropyl, 2,2-didecyl Propyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-mercaptopentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl 1,1,3-dimercaptobutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl 1,1,2-trimethylpropyl, 1,2, | 2 -trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methyl

| propyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentanyl, 1-propylbutyl, octyl, decyl, decyl . The dentate alkyl group is an alkyl group as defined above which is partially or wholly halogenated by one or more halogen atoms, especially fluorine and chlorine. Preferably, there are from 1 to 3 functional atoms, and particularly preferably a difluoroindenyl or trifluoroindenyl group. The above statements for alkyl and haloalkyl groups are applied to the corresponding groups of alkyl and functional alkyl groups, such as alkoxy groups, halogenated dairy groups, sulfur-burning groups, functional sulphur groups, and calcites.

Page 10 1246886 丨五、发明说明(5) Brewing base and burning turtle base. The i-alkenyl group contains a straight chain and a branched alkenyl group. It is preferably a linear or branched c3_12 alkenyl group and especially a C3_6 alkenyl group. Examples of alkenyl groups are 2-propenyl, 2-butenyl, |3-butenyl, 1-indolyl-2-propenyl, 2-methyl-2-propenyl, 2-pentene; 3-pentenyl, 4-pentenyl, 1-decyl-2-butenyl, 2-mercapto-2-butyridyl, 3-methyl-2-butenyl, 1-indenyl- 3-butyryl, 2-methyl-3-butenyl, 3-mercapto-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-diindenyl- 2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-decyl-2-pentenyl, 2-mercapto-2-pentyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3 -pentenyl, 3-methyl-3-pentenyl, fluorenyl 4-mercapto-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentene , 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl; -2 -butyldinyl, 1,1-diindenyl-3-butadiene 1,1,2-didecyl-2-butanyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-: I-dimethyl-3-butanyl, 2,2-dimethyl-3-butanyl, 2,3-diindenyl | -2 - butyzanyl, 2,3-dimercapto-3-butylenyl, 1-ethyl-2-butanyl, 丨1-ethyl-3-butanyl, 2-ethyl-2 Butyryl, 2-ethyl-3-butenyl], 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl blood | and 1- Ethyl-2-methyl-2-propanyl 'especially 2-propenyl, 2-butenyl, 3-mercapto-2-butenyl and 3-methyl-2-pentenyl . The alkenyl group may be partially or fully converted via one or more halogen atoms, especially fluorine and gas. The dilute group preferably has 1 to 3 halogen atoms. ! Alkynyl groups include straight chain and branched alkynyl groups. Preferably linear and branched c3_12 alkynyl

Page 11 1246886 i—— ^ ~ ~ i

发明五、发明说明(6) I ! and especially C3_6 alkynyl. Examples of alkynyl groups are 2-propynyl, 2-butynyl, 3- | j I -butanyl, 1-methyl-2-propenyl, 2-pentopenyl, 3-pentyl, 4- Alkenyl, alkynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-mercapto-2-butynyl, 1,1-didecyl-2-propyne , 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1- Methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-mercapto-3-pentynyl, 2-mercapto-4-pentynyl, 3-methyl-4-pentane Alkynyl, 4-methyl-2-pentynyl, 1,2-dimethyl-2-butynyl, 1,1-dimercapto-3-butynyl, 1,2-didecyl- 3-butyl group, 2,2-dimercapto-3-3-butanyl, 1-ethyl-2-butanyl, 1-ethyl-3-butanyl, 2-ethyl-3-but Fast group and 1-ethylindol-1-methyl-2-propynyl. The above statements for alkenyl groups and their halogen substituents and p-alkynyl groups are applied to the dilute oxy and alkynyloxy groups in a corresponding manner.丨 | The cycloalkyl group is preferably a c3_6 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group or a cyclopentyl group.

! or cyclohexyl. If the cycloalkyl group is substituted, it preferably has 1 to 3 alkyl groups as a substituent. ! ! ! The cycloalkenyl group is preferably a C4-6 cycloalkenyl group such as a cyclobutenyl group, a cyclopentenyl group or a cyclohexenyl group. If the cycloalkenyl group is substituted, it preferably has 1 to 3 (^-4 alkyl groups as a substituent. The cycloalkyloxy group is preferably a C5_6 cycloalkoxy group such as a cyclopentyloxy group or a cyclohexyloxy group; The cycloalkoxy group is preferably substituted with 1 to 3 alkyl groups as the substituent I group. The cycloalkenyloxy group is preferably a c5-6 cycloalkenyloxy group such as a cyclopentenyloxy group or a cyclohexeneoxy group I. When the alkenyloxy group is substituted, it preferably has 1 to 3 Cj_4 alkyl groups as

Page 12 1246886 V. INSTRUCTIONS (7) Substituents. The aryl group is preferably a phenyl group. If A is a phenyl group, it may have 1, 2 or 3 of the above substituents at any position. Preferably, the substituents are independently selected from the group consisting of alkyl, difluoromethyl, trifluoromethyl and halogen, especially chlorine, bromine and iodine. More preferably, the phenyl group has a substituent at the 2-position. If A is a 5-membered heterocyclic ring, it is especially furyl, thiazolyl, pyrazolyl, sulphate, sulphate, thienyl, tridecyl or thiadiinyl or its corresponding dihydrogen or Tetrahydrogen derivative. Preferred is thioxanyl or carbazolyl. If the oxime is a 6-membered heterocyclic ring, especially a pyridyl group or a group of the formula:

γ wherein one of the X and Y groups is 0, S or NR12, wherein R12 is fluorene or alkyl, and the other of the X and Y groups is CH2, S, SO, S02 or (10)12. The dashed line indicates the presence or absence of a double bond. The 6-membered aromatic heterocyclic ring is preferably a pyridyl group, especially a 3-pyridyl group or a group of the formula:

(A3) wherein X is CH2, S, SO or s〇2. The above heterocyclic group may or may not have 1, 2 or 3 of the above substituents,

Page 13 1246886 V. Description of the invention (8) Substituents such as alkyl, dentate, difluoromethyl or COSCO are preferably selected independently of each other. i ! A is better for the following formula: R7,

CC R3

(A2) -R8

(A1) N

R6 (A5) (A7) CH3 wherein R3' R4, R6, R7, R8 and R9 are independently of each other hydrogen, alkyl, especially methyl, halogen, more particularly gas, CHF2 or 叮^. The R1 group in the formula I is preferably a hydrogen atom. The R2 group in the formula 1 is preferably a phenyl group. R2 preferably has at least one substituent in particular at the 2-position. The substituent (or substituents) is preferably selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkenyl group, a south group, and a phenyl group. The substituent of the R2 group can be further substituted. The aliphatic or cycloaracene substituents may be partially or completely dentated, especially fluorinated or vaporized. It preferably has 1, 2 or 3 fluorine or chlorine atoms. If the substituent of the R2 group is a stupid group, the stupid group is preferably substituted by 1 to 3 halogen atoms (especially a gas atom) and/or preferably substituted by an alkyl group and an alkoxy group. - The position is substituted by a south atom, that is, the special base of the base of the base is a stupid base substituted by a halogen. The R2 group may also be condensed with a saturated 5 member ring, wherein the ring portion may have 1 to 3 alkyl substituents. In this example, U is, for example, a fragmented base, a fully charged group, and a morden base. Better

Page 14 1246886 I. V. INSTRUCTIONS (9) ! I is a full base and a 2-sound full base, especially attached to the nitrogen atom via a 4-position.丨 According to a preferred embodiment, the composition of the invention comprises A in formula I as defined below

Compound of I as Siamine compound: phenyl, pyridyl, dihydropyranyl, dihydrothylthiopyranyl, dihydrothylthiopyranyl oxide, dihydrothiopyranyl dioxide, furyl, thiazole Or pyrazolyl or oxazolyl, wherein the group may have 1, 2 or 3 substituents independently selected from the group consisting of alkyl, halo, difluoromethyl and trifluoromethyl. 1 According to a further preferred embodiment, A is: pharyngeal bite - 3 - base ' which can be in the 2-position with or without halogen, methyl, and

I thiol, trifluoromethyl, methoxy, methylthio, sulfinyl or methanesulfonyl; phenyl, which may be at the 2-position with or without methyl, trifluoromethyl, Gas, | bromine, or moth substitution; 2-methyl-5,6-dihydropyran-3-yl; 丨2-mercapto-5,6-dihydro-1,4-thiopyran-3- Or a 4-oxide or I 4 , 4 -dioxide; ! ΐ 2 -mercaptopurin-3-yl which may be substituted at the 4- and/or 5-position with or without methylhydrazine; Ru thiazol-5-yl which may be substituted at the 2- and/or 4-position with or without thiol, chloro, !difluoroindolyl or trifluoromethyl; thiazol-4-yl, which may be in 2 - and / or 5 - position with or without methyl, chloro, ...: difluoroindenyl or trifluoromethyl; 1-methyl indol-4-yl, which may be in 3 - and / or 5 - Position or not

Page 15 1246886 V. Description of the invention (ίο) base, gas, difluoromethyl or trifluoromethyl substituted; oxazol-5-yl which may or may not be methyl at the 2- and/or 4-position Or chlorine substituted. According to still further preferred embodiments, the composition of the present invention comprises a compound of the formula I wherein R2 is a phenyl group which may be substituted with or without 1, 2 or 3 of the above substituents as a guanamine compound: According to a further preferred embodiment, The composition of the invention includes a compound of the formula I wherein R 2 is a phenyl group having the following substituent at the 2-position as a guanamine compound: C 3_6-alkyl, C 5-6-cycloalkenyl, C 5-6-cycloalkoxy, cycloalkenyloxy, Wherein the group may be substituted by 1, 2 or 3 Cy-alkyl groups, which are 1 to 5 halogen atoms and/or 1 to 3 independently selected from the group consisting of Ch-alkyl groups, (^_4- a halogen group, (^_4-alkoxy group, -halo alkoxy group, (V4-alkylthio group and c^-haloalkane group substituted by a group, 苟7 full base or a ruthenium J full base, which can be Or without 1, 2 or 3 (^_4 - alkyl group substitutions. According to further preferred embodiments, the composition of the invention comprises a compound of formula Ia as an acid amine compound:

(la) where A is

Page 16 1246886 V. Description of invention (π)

(X R3

(A2) R4 (Al) 〇, Η 3 (A3) R5 R5/\〇/\CH3 (A4) R9, RVS- N- (A5) R6 R7 — (A6) R4 CH3-N, R8 (A7)

R9 sulfur, sulfhydryl or a carboxylic acid group (S 02), • fluoromethyl, trifluoromethyl, gas, bromine or iodine X is a methyl group R3 is a fluorenyl group, and R4 is a trifluoromethyl group or a chlorine group. R5 is hydrogen or methyl, fluoroindenyl or chloro R6 is methyl, difluoromethyl R7 is hydrogen, fluorenyl or chloro, R8 is methyl, difluoromethyl or trifluoromethyl, R9 is hydrogen, A a group, a difluoromethyl group, a trifluoromethyl group or a gas, and R1Q is (^_4 - leukoyl group, Ch-homoyloxy group, Ch-sulfuryl group or halogen. According to a particularly preferred embodiment, the composition comprises the formula Ib Compounds as guanamine compounds: Ϊ

I 1246886 V. INSTRUCTIONS (12) CO-NH R4 Rn

Db) wherein R4 is halogen, and R11 is phenyl substituted by halogen. A particularly preferred mixture of the invention comprises a compound of the formula: as component I:

Useful guanamine compounds of the formula I are described in EP-A-5 4 5 0 9 9 and 5 8 9 3 0 1, all of which are incorporated herein by reference. The preparation of the guanamine compound of the formula I is known, for example from EP-A-5 5 5 9 9 i | or 5 8 9 3 0 1 or can be carried out in a similar manner.

曱 胺 II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

No. 243, 2 2 (1 9 9 5 )], its preparation method and its role in resisting harmful fungi have also been

Page 18 1246886 V. Description of invention (13) Know. The compounds of formula I I I are also known per se. The first preferred class of indoleamine derivatives is a compound of formula I I:

Rl3〇

(11工' wherein R13 is as defined above, and X is halogen Ί-4 alkyl or Ci_4-homoyl. Such compounds and their preparation are described, for example, in EP-A-0 06 1 0 7 6 4 and EP-A - 0 3 9 8 Q72, which are incorporated herein by reference. More preferably, the indoleamine derivative is a compound of formula II;

Wherein R13 is as defined above. Such compounds and their preparation are described, for example, in DE-A-4 3 2 1 8 97 and WO-A-9 6/0 7 6 3, which are incorporated herein by reference. Preferably, R13 in formula I II is an isopropyl compound. The second butyl group and the third butyl group are similarly, wherein the compound of the formula III is preferably wherein R14 is an α-alkyl group, a /3 -1 group and a phenyl group, and the phenyl group is subjected to a gas and an oxy group at the 4-position. Replacer. q _4 -alkyl or q-burning, especially a compound of formula III wherein R14 is /3 -yl, 4-chlorophenyl, 4-nonylphenyl and -nonyloxyphenyl

Page 19 1246886 丨 V. INSTRUCTIONS (14) ! Preferred examples of the indoleamine which can be used in the present invention are summarized in the following Table 2 Table 2 No. R13 R14 III.l Isopropyl III.2 Isopropyl 4- Chlorophenyl III.3 Isopropyl 4-mercaptophenyl III.4 Isopropyl 4-nonyloxyphenyl III.5 Second butyl β-Le 111.6 Second butyl 4-chlorophenyl III.7 Second butyl t methylphenyl III.8 second butyl 4-methoxyphenyl III.9 third butyl/5-based III.10 tert-butyl 4-chlorophenyl III· 11 Tributyl 4-mercaptophenyl III.12 The third butyl 4-oxime phenyl group is a compound π 1. 2 and III · 9. From the structure of the compound of the formula II I, it can be seen that the compounds have two asymmetrically taken fossil carbon atoms. Thus the compound can be used in the mixture of the invention as a mixture of different isomers or as a pure isomer. In a more preferred embodiment, a compound in which the amino acid moiety is formed from alkoxycarbonyl-L-proline (S configuration) and the phenethylamine moiety or the ethylamine moiety has an R configuration can be used. Such a compound can be represented by the formula I I I a : h3c-ch-ch3 τ ch3 (R) H H , Ri4 (IHa) (S)

Page 20 w 1246886 V. INSTRUCTIONS (15) wherein R13 and R14 are as defined for the compound of formula II. The preparation of the preferred isomers of the formula I I a is carried out in a manner similar to that described in the earlier German patent application DE-A-195 31 814. The disclosure of this application is incorporated herein by reference. The isomeric pure compound of the formula Ilia can be prepared starting from a suitable L-proline-based amine mercaptocarboxylic acid v I according to a method known per se. For example, it can be obtained by reacting an amine-mercaptocarboxylic acid VI with an amine VII (this reference _ Houbsn-Wey 1 shows: Houben- ffeyl, Methoden der Organ i schen Chemie, 4th edition, Thi eme Ver1ag ,

Stuttgart): r^3〇

(VI)

H i ch3 (VII) Aminocarboxylic acid VI is known or can be prepared by known methods, in particular starting from the amino acid L-valine (cf. "Houben-Weyl", Volume 15/1) , pp. 4 6 - 3 0 5, especially pages 1 17-125).

I

Iamine VII is also known or readily available (cf. Organikum, V EB | Deutscher V e r1ag der Wissenschaften, 15th edition, I Berlin, 1977, p. 610 ff.; nHouben-Weyln, Vol. 15/1, I Pages 648-665 Indian J. Chem. 10, p. 366 (1972); J. Ain. Chem. S〇c. 58, pp. 1808 – 1811 (1936)) 消 by amine VII racemate , R isomer can be isolated by itself, for example,

Page 21, for example, 1246886 丨 、 发明 发明 、 、 、 、 、 、 、 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如This method is preferably activated by first converting the amine mercaptocarboxylic acid V I to a carboxyl group; the derivative 'in particular, the cyanide or anhydride (refer to Tetrahedron i

Letters, Vol. 18, No. 1 5 9 5- 1 5 9 8 (1 9 73 ) or nHouben-Weyl", Vol. 15/1, pp. 28-32), the derivatives are further in the presence of a base with an amine VII reaction. Suitable for the preparation of a slow-acting activated mercapto cyanide such as a carbamate carboxy oxime V is reacted with a cyano-I 曰 曰, especially in an inert solvent such as tetrahydroanthracene. Reacts in the south toluene. The preparation of the carboxylic acid anhydride is preferably carried out by reacting an amine carbenylcarboxylic acid v with a gas carboxylic acid / isobutyl formate in the presence of a base and, if appropriate, in an inert agent such as toluene or tetrahydrofuran. ^ The reaction of the amine VI I with the carboxyl-activated amine carbenylcarboxylic acid VI is preferably carried out in dioxane, tetrahydrofuran or methyl. Ridgeback 1 amine V II can also be used as an assay. In this case, it is usually obtained from the crude preparation of this method step. m, sulfhydryl-activated amines suitable for the production of amine-based basal acid VI. Sword and alkali are reacted in a one-pot process, and if appropriate, the base 四(4)uu. Is the operation separate from the amine? Compound IV. 1 is purchased under the common name BenaU (GalbenTM). ^义商°. 名嘉笨 Compound I V · 2 takes you as the common name Oufu (ofurace) or trade name Saita

1246886

I I

i. Description of the Invention (17) I (CeltanTM) P was purchased as a mixed compound with cymoxanil and folpet. Compound IV. 3 is commercially available under the common name metal axyl or the trade name Ridomi 1τΜ. Compound 1 ¥.4 is commercially available under the common name Fluorah (丨1^318乂71) or the trade name FongarideTM. Compound IV. 5 is commercially available as a common name oxadixyl or as a mixture with a copper salt under the trade name SandofanTM C. Methods of preparing compounds of formula IV are known to those skilled in the art and need not be described in detail. "丨 Compound V (US-A-3, 95 7, 847; common name: Simmonin), its preparation method and its activity against harmful fungi are also known. In order to exhibit synergistic activity, even a small amount of the imine compound of the formula is sufficient, and it is preferred to use a weight ratio of the guanamine compound to the compound II and/or the compound III to V i in the range of 20:1 to 1:20, especially 10:1 to 1:10. I 1 | When preparing this mixture, it is preferred to use pure active ingredients I and II and/or 丨|; i III to V, in which other active ingredients against harmful fungi or other pests, such as insecticides, may be mixed. Agent 'Acaricide or nematicide, or other herbicide or oyster long regulating active ingredient or fertilizer. 4

I Compounds I and II and/or mixtures of I II to V, or simultaneously (either together or separately) Compounds I and II and/or III to V exhibit significant effects on a wide range of phytopathogenic I | sex fungi Activity, especially for Asconiycetes, Basidiomycetes, Phycomycetes, and Deuteromycetes. It has

Page 23 1246886 :-——- ! ---~_______________ V. INSTRUCTIONS (18) These are systemic and therefore also useful as foliar- and soil-acting bactericidal agents. 〃 For various crops such as cotton, vegetable species (such as courgette, kidney bean, confession, potato and gourd), barley, pasture, oak, incense, coffee, corn, fruit species, rice, rye, soybean, grape, wheat The control of a large number of fungi in decorative plants, sugar cane and various seeds is particularly important. It is especially suitable for the control of the following phytopathogenic fungi: Erysiphe graminis, Erysiphe cichoracearum and Sphaerotheca fuliginea, white stalk of apple Shell (Podosphaera leucotricha), grape nuclei (U ncinu 1 aneca ΐ〇r ), Puccinia species, cotton, rice and grass Rhizoctonia species, shells and Ustilago species of sugarcane, Venturia inaequalis (Icebeat disease), H e 1 minth 〇s ρ 〇rium species, wheat stalk (S eptoria η odorum ), strawberries, vegetables, decorative plant mites and Botrytis cinerea (Gray mold), groundnuts; Cercospora arachidicola, wheat and barley! /j, 4>KPseud〇cerc〇sp〇rella herpotrichoides), Pyricularia oryzae, pathogenicity of potato and tomato | Phytophthora infesta Ns), grape unicorn mold | ( P 1 a s m 〇 p a r a v i t i c ο 1 a ), hop and myrtle cream

I I (Pseudoperonospora) species, Alternaria species of vegetables and fruits, fragrant, globular _ (Myc〇sphaerella) species

Page 24 1246886 I. INSTRUCTIONS (20) Liquids, pastes, powders, substances or particulate matter for dissemination, and applied by spraying, atomizing, dusting, spreading or sprinkling water. The state of use varies depending on the intended purpose; in any case, the mixture of the present invention should be as painfully distributed as possible and uniform. The formulation is prepared in a known manner, for example by using a solvent and/or a carrier and, if necessary, using an emulsifier and a dispersing agent to dilute the active ingredient, if water is used.

|Alternative solvents can also be used as diluents. Suitable adjuvants for this purpose are essentially as follows: solvents such as aromatics (such as xylene), gasified aromatics (such as gas benzene), alkanes (remaining mineral oil), alcohols (such as methanol, butanol), ketones Classes (such as cyclohexanone), amines (such as ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (such as kaolin, clay, talc, chalk) and ground synthetic minerals (such as fine particle oxidation Emulsifiers such as nonionic and anionic emulsifiers (such as polyoxyethylene fatty alcohol ethers, alkane sulfonates and aryl sulfonates) and dispersing agents such as wood sulfite waste liquids and methyl esters Cellulose. Suitable surfactants are aromatic sulfonic acids such as wood-, phenol-, s- and s-butyl sulphonic acid: metal salts, soil-measuring metal salts and ammonium salts, fatty acids, burning | Metal salt, soil test metal salt and ammonium salt, base base | lauryl ether and fatty alcohol sulfate, and sulfated 16-, 17- and octadecane I alcohol salts, or fatty alcohols Alcohol ether salt, sulfonated "1 and its derivatives with 曱ί

A condensate of condensate, sulphate or sulphate and age and formic acid, polyoxyethylene I octyl phenol ether, isooctyl ethoxylate, octyl or decyl-phenol, alkylphenol poly I alcohol ether, tributyl phenyl polyglycol ether, alkyl aryl polyether alcohol, isotridecane! alcohol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or Polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, wood sulfite waste liquid or methyl cellulose.

Page 26 1246886 V. INSTRUCTIONS (21) Powders, materials for dispersion and powders can be prepared by mixing or grinding together a compound I or I I, or a mixture of compounds I and I I, with a solid carrier. Granules (e.g., coated granules, wet granules or homogeneous granules) are generally prepared by incorporating the active ingredient (or active ingredient) onto a solid carrier.

The filler or solid carrier is, for example, ore such as cerium oxide, cerium, cerium, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, shixia, sulfuric acid, magnesium sulfate Oxidizing towns, grinding synthetic materials and fertilizers such as sulphuric acid clocks, cans, sulphate, urea, and plant-derived products such as flour, bark powder, wood flour and sturdy shell powder, cellulose powder or other solid carrier. The formulation generally comprises from 0.1 to 9.5 wt%, preferably from 0.5 to 90 wt% of one of the compounds I and I and/or I I to V or a mixture of the compounds I and I I and/or I I to V. The active ingredient is used in a purity of from 90% to 100%, preferably from 915% to 100% (as determined by NMR spectroscopy or HPLC). Compounds I and II and/or III to V, mixtures or corresponding formulations may be used to treat harmful fungi, or a fungicidally effective amount of compounds I and II and/or III to V (in the case of application, respectively) for the treatment of harmful fungi, A habitat, or plant, seed, soil, area, material, or space that is intended to control fungi.

Administration can be carried out before and after infection with harmful fungi. Examples of such preparations including active ingredients are: I. A solution containing 90 parts by weight of active ingredient and 10 parts by weight of N-methylpharyngeal 17 calcined; this solution is preferably used as a microdropper; II. 20% by weight Addition of active ingredient, 80 parts by weight of xylene, 10 parts by weight of 8 to 10 moles of ethylene oxide and 1 mole of N-monoethanolamine

Page 27 1246886 V. INSTRUCTIONS (22) | Mixture of 5 parts by weight of calcium dodecylbenzenesulfonate, 5 parts by weight of 40 moles of epoxy I ethane and 1 mole of anaesthetic adduct By dispersing the solution finely in water to obtain a dispersion; II I. containing 20 parts by weight of active ingredient, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of 40 mole of epoxy An aqueous dispersion of an adduct of ethane and 1 mol of castor oil; IV. a mineral oil containing 20 parts by weight of active ingredient, 25 parts by weight of cyclohexanol, 65 parts by weight of boiling point 2 1 0 to 2 80 ° C And an aqueous dispersion of 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil; V. 80 parts by weight of active ingredient, 3 parts by weight of ground in a clock mill a mixture of 1 isobutylacyl-1-sulfonate sodium salt, 10 parts by weight of a sodium sulfonate sodium salt obtained from a sulfite waste liquid, and 7 parts by weight of a pulverized tannin; by finely distributing the | mixture to obtain a spray in water a mixture of mist; i VI. 3 parts by weight of active ingredient and 97 parts by weight of intimately mixed fine kaolin; this dust comprises 3% by weight of active ingredient; VII. 30 weight An intimate mixture of the active ingredient, 92 parts by weight of pulverized tannin and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silicone; this formulation imparts good adhesion to the active ingredient; 丨V II I. 40 parts by weight of active ingredient, 10 weight a portion of the aqueous salt of the mixture of the naphthenic acid/urea/ruthenium condensate, the sodium salt of the compound, the 2 parts by weight of the Shiqi gum and the 48 parts by weight of water; the dispersion can be further diluted; IX. 20 parts by weight Active ingredient, 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of a fatty alcohol polyglycol ether, 20 parts by weight of a sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, and 88 parts by weight of a mineral oil A stable oily dispersion.

Page 28 1246886 i. V. INSTRUCTION (23) Example of Use The synergistic activity of the mixture of the present invention is demonstrated by the following experiments: The active ingredients (respectively or together) are formulated to contain 63% by weight of cyclohexanone and 27% by weight of emulsified 10% emulsion in a mixture of agents and diluted with water to the desired concentration. I - was assessed by measuring the percentage of infected leaf area. These percentages are converted into efficiencies. The efficiency (W) is calculated using the Abb's (A b b 〇 1;' s ) program as follows:

W=U- a ) -100//3 α corresponds to % of the fungal infection of the treated plants, and /3 corresponds to the % of the fungal infection of the untreated plants. An efficiency of 0 indicates that the treated plants are infected to an extent equivalent to the untreated control plants; an efficiency of 100 indicates that the treated plants are not infected. The expected efficiency of the active ingredient mixture was determined using Colby's program [R.S. Colby, Weeds 15, i 20-22 (1967)] and compared to the observed efficiency of I. | Kirby program: E=x + y- X ·γ/100

When E E is a mixture of active ingredients A and B at concentrations a and b, the expected efficiency is expressed as % of the control group. X When the active ingredient A of the concentration a is used, the efficiency of 丨 is expressed as % of the untreated control. y When the active ingredient B of the concentration b is used, the efficiency of 丨 is expressed as % of the untreated control. | Use Example 1 - Activity against tomato against Phytophthora infestans

Page 29 1246886 I V. INSTRUCTIONS (24) i Aqueous suspension spray prepared from a stock solution containing 10% active ingredient, 63% cyclohexanone and 27% emulsifier” G r 〇/3 e F 1 Eischt 〇mat; e π species of potted plants from the top to the extent of dripping. The next day, the leaves were infected with the aqueous suspension of Phytophthora infestans. The plants were then placed in a water vapor saturation chamber at 16 - 18 °C. After 6 days, the untreated tomatoes were withered but the infected control plants developed to the infection rate and the degree of % was visually determined. The compound I used was the following:

Table 1 Example Active Ingredient (in ppm) Active ingredient concentration in spray solution (ppm) Efficiency of untreated control % 1C Untreated 0 (100% infection) 0 2C Compound 1.1 3.1 0 3C Compound 1.2 3.1 0 4C Compound IV .3 3.1 0 page 30

Claims (1)

O:\56\56404-940729.ptc Page 33 1246886 9c/Yearly September 曰Revision _ Case No. 87121221 6. Patent application scope or c) imipenem of formula III: H3C-CH-CH3 〖| 〇CH3 ' R13〇—C—NH—CH—C—NH—CH—wherein R13 is C3_4 alkyl, and R14 is naphthyl or phenyl, wherein phenyl is bonded to the 4-position via a halogen atom, an alkyl group or a Cw alkoxy group. Substituting, or d) at least one active ingredient of the formula IV · 1 to IV · 5: 〇 ch3 II 1 jj CH2 a C CH C〇2 CH3 h3c Ch3 (IV.1) O:\56\56404-940729.ptc Page 34 1246886 O:\56\56404-940729.ptc Page 35 1246886 _ Case No. 87121221 VI. Scope of Application 曰 Amendment 3. The fungicidal mixture according to item 1 or 2 of the patent application is adjusted into two parts, one of which The guanamine compound I is included in a solid or liquid carrier, and the other portion is included in a solid or liquid carrier selected from the group consisting of the compounds of the formula Ila, the formula lib, the formula III, and the formulae IV.1 to IV.5. A method for controlling harmful fungi, comprising treating a fungus with a fungicidal mixture according to claim 1 or 2, a habitat thereof, or a material, plant, seed, soil, region to be protected from the fungus Or space, wherein the active ingredient guanamine compound I and a compound selected from the group consisting of formula II a, formula II b, formula III, and formula IV.1 to IV. 5 can be simultaneously or continuously administered - O:\56\56404-940729.ptc第36页